Hirshfeld surface and theoretical studies of 2,2,2-trichloro-N,N-bis(2-(2,2,2-trichloroacetamido)phenyl)acetamide compound European Journal of Chemistry 10 (4) (2019) 323-335 European Journal of Chemistry View Journal Online View Article Online Hirshfeld surface and theoretical studies of 2,2,2-trichloro-N,N-bis(2-(2,2,2- trichloroacetamido)phenyl)acetamide compound Immihan Sezen Aydogdu 1,*, Ilkay Gumus 2 and Hakan Arslan 1 1 Department of Chemistry, Faculty of Arts and Science, Mersin University, Mersin, 33343, Turkey immihansezen@gmail.com (I.S.A.), hakan.arslan@mersin.edu.tr (H.A.) 2 Department of Basic Sciences, Faculty of Maritime, Mersin University, Mersin, 33343, Turkey ilkay.gumus@mersin.edu.tr (I.G.) * Corresponding author at: Department of Chemistry, Faculty of Arts and Science, Mersin University, Mersin, 33343, Turkey. Tel: +90.505.4574736 Fax: +90.324.3610047 e-mail: immihansezen@gmail.com (I.S. Aydogdu). 10.5155/eurjchem.10.4.323-335.1920 Received: 24 August 2019 Received in revised form: 17 October 2019 Accepted: 22 October 2019 Published online: 31 December 2019 Printed: 31 December 2019 The vibrational frequencies, atomic charges and the related properties of the 2,2,2-trichloro- N,N-bis(2-(2,2,2-trichloroacetamido)phenyl)acetamide (H2LNNN) were investi-gated by Ab- initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods such as BLYP, B3LYP, B3PW91 and mPW1PW91 functionals with 6-31G(d,p) and 6-311G(d,p) basis sets. The experimentally determined parameters were compared with those calculated theoretically and they were found to complement each other with a very good correlation. The theoretical vibrational spectrum of H2LNNN molecule was interpreted by means of potential energy distributions using the SQM 2.0 program. The Hirshfeld surface analysis was carried out to discuss the role of the hydrogen bonds and other intermolecular contacts in crystal lattice. Hirshfeld surface analysis revealed the occurrence of Cl⋯H, Cl⋯Cl, Cl⋯C, H···H, O⋯H, C···H and Cl···π interactions that display an important role on the crystal packing stabilization of the compound. Acetamide Vibration spectrum Ab-initio calculations Redox active compound Density functional theory Hirshfeld surface analysis Cite this: Eur. J. Chem. 2019, 10(4), 323-335 Journal website: www.eurjchem.com 1. Introduction The redox active compounds containing amide donors can be modified according to specific needs and most of them have catalytic activity [1-9]. So, in recent years, most of the resear- chers focused on these types of compounds. Numerous studies have been devoted to investigate how the reactivity of transition metals is affected by a small change in the electron donor property of the ligand [3,4,6]. Redox active compounds have a wide range of uses [2-20]. For complexes of these compounds, a detailed spectroscopic, magnetic, structural and theoretical investigation is used to detect formal oxidation states in metal centers. Recent studies have focused on investigating the importance of the skeleton on unit reactivity rather than understanding the electronic structures of comp- lexes. In the light of above-mentioned information, our research group focused on the study of redox active compounds. One of them is 2,2,2-trichloro-N,N-bis(2-(2,2,2-trichloroacetamido) phenyl)acetamide (H2LNNN). The crystal structure of H2LNNN was obtained using single crystal X-ray diffraction studies [21,22]. Nonetheless, to the best of our knowledge, both Ab- initio studies of the vibrational spectra in the gas phase and the Hirshfeld surface analysis of H2LNNN have not been reported previously. Thus, we calculated the geometric parameters and vibrational frequencies of H2LNNN in the ground state to distinguish the fundamentals from the experimental geometric parameters and vibrational frequencies by HF, BLYP, B3LYP, B3PW91 and mPW1PW91 methods with the standard 6-31G(d,p) and 6-311G(d,p) basis sets. A detailed interpretation of the vibrational spectra of H2LNNN molecule has been made on the basis of the calculated potential energy distribution (PED). We also report detailed analysis of intermolecular interactions by Hirshfeld surfaces analysis. The surfaces are mapped with dnorm, 2D-fingerprint plots, shape-index and curvedness properties. The Hirshfeld surface and associated fingerprint plots of H2LNNN molecule have also provided a platform for the evaluation of the contribution of different atom···atom contacts, which contribute to the packing of the molecules in solids. 2. Experimental 2.1. Instrumentation ABSTRACT RESEARCH ARTICLE KEYWORDS European Journal of Chemistry ISSN 2153-2249 (Print) / ISSN 2153-2257 (Online) – Copyright © 2019 The Authors – Atlanta Publishing House LLC – Printed in the USA. This work is published and licensed by Atlanta Publishing House LLC – CC BY NC – Some Rights Reserved. http://dx.doi.org/10.5155/eurjchem.10.4.323-335.1920 http://dx.doi.org/10.5155/eurjchem.10.4.323-335.1920 https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.10.4.323-335.1920&domain=pdf&date_stamp=2019-12-31 http://www.eurjchem.com/ http://dx.doi.org/10.5155/eurjchem.10.4.323-335.1920 mailto:immihansezen@gmail.com mailto:hakan.arslan@mersin.edu.tr mailto:ilkay.gumus@mersin.edu.tr mailto:immihansezen@gmail.com http://www.eurjchem.com/ https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.10.4.323-335.1920&domain=pdf&date_stamp=2019-12-31� 324 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 5001000150020002500300035004000 R el at iv e Tr an sm itt an ce , A rb . u ni ts Wavenumber, cm-1 (a) (b) Figure 1. (a) Experimental and (b) theoretical FT-IR spectrum of 2,2,2-trichloro-N,N-bis(2-(2,2,2-trichloroacetamido)phenyl)acetamide compound. NO2 NH2 NO2 F N H NO2 NO2 DMSO KOtBu N H NO2 NO2 N H NH2 NH2 Pd/C H2 N H NH2NH2 Cl O N HN O NHO 3 Cl Cl Cl Cl ClCl O Cl Cl Cl Cl Cl Cl Scheme 1. The synthetic route for 2,2,2-trichloro-N,N-bis(2-(2,2,2-trichloroacetamido)phenyl)acetamide. The NMR spectra were recorded in Acetone-d6 solvent on Bruker Avance III 400 MHz NaNoBay FT-NMR spectrophoto- meter using tetramethylsilane as an internal standard. The room-temperature-attenuated total reflection Fourier trans- form infrared (FT-IR ATR) spectrum of 2,2,2-trichloro-N,N- bis(2-(2,2,2-trichloroacetamido)phenyl)acetamide compound was recorded using a Perkin Elmer Spectrum 100 series spectrometer with a ATR prism (4000-525 cm-1; number of scans: 200; resolution: 1 cm-1) (Figure 1). 2.2. Synthesis The solvents and chemicals used in the study were commercially obtained from companies such as Merck, Aldrich and Alfa-Aesar and were used without further purification. Precursor materials bis(2-nitrophenyl)amine and bis(2-amino phenyl)amine were prepared according to the previously published method (Scheme 1) [21-24]. A solution of trichloro acetyl chloride (10 mmol) in acetonitrile (50 mL) was cooled to 0 °C under nitrogen atmosphere. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 325 (a) (b) Figure 2. The optimized geometry of H2LNNN molecule calculated at B3LYP/6-311G (d,p) level (a) and a view of the molecular structure of H2LNNN molecule with displacement ellipsoids drawn at the 50% probability level (b) [21]. Then, bis(2-aminophenyl) amine (5 mmol) was slowly added to this cold solution over 3 hrs. The mixture was stirred at 0 °C for 3 hrs and the mixture temperature was allowed to slowly rise to room temperature. The mixture was stirred at room temperature for 24 hrs and the solvent was removed under vacuum. The final product was crystallized by slow evaporation of the concentrated solution in hot acetone (Scheme 1) [21,22]. 2,2,2-Trichloro-N,N-bis(2-(2,2,2-trichloro acetamido)phenyl) acetamide (H2LNNN): Color: White. Yield: 43%. 1H NMR (400 MHz, Acetone-d6, δ, ppm): 10.23 (s, 2H, NH(CO)), 7.82-7.42 (m, 8H, Ar-H). 2.3. Calculation details The Gaussian 16W program package on a double Xeon/3.2 GHz processor with 16 GB Ram was operated to obtain all calculations [25]. BLYP, B3LYP, B3PW91, mPW1PW91 and HF methods with the standard 6-31G(d,p) and 6-311G(d,p) basis sets were applied to optimize the molecular structure of 2,2,2- trichloro-N, N-bis(2-(2, 2, 2-trichloroacetamido)phenyl) acet- amide molecule in the ground state. These methods were also used to calculate the vibrational frequencies. The frequency values computed at these levels contain known systematic errors [26]. Scaling factor values of 0.9614, 0.9679, 0.9573, 0.9631, 0.9945, 0.9934, 0.8992, 0.9051, 0.9500 and 0.9567 for B3LYP/6-31G(d,p), B3LYP/6-311G(d,p), B3PW91/6-31G(d,p), B3PW91/6-311G(d,p), BLYP/6-31G(d,p), BLYP/6-311G(d,p), HF/6-31G(d,p), HF/6-311G(d,p), mPW1PW91/6-31G(d,p) and mPW1PW91/6-311G(d,p), respectively, can be used to correct these discrepancies [27-33]. Also, optimal scaling factors were calculated for all analyzed methods. The GaussView 6.0 grap- hical interface of the Gaussian program, which is an animation option that provides a visual representation of the shape of the modes of vibration, provides a way of assigning the calculated wavenumbers [34]. The SQM procedure has been widely used in the assignment of bands of vibrational spectra due to being a highly successful and well established technique in refining the computerized vibration frequencies to match the experi- mental values better [35]. So, the vibrational modes were determined according to the potential energy distribution analysis using the SQM program [36]. Using the PAVF 1.0 program, the performance of the used method was quantita- tively characterized [37]. The population analysis has also been performed by the natural bond orbital method [38] at B3LYP, BLYP, B3PW91, mPW1PW91 and HF /6-31G(d,p) and 6-311G(d,p) level of theory using the natural bond orbital (NBO) program [39] under the Gaussian 16W program package. 2.4. Hirshfeld surfaces analysis Analysis of Hirshfeld surfaces and their associated two dimensional fingerprint plots of 2,2,2-trichloro-N,N-bis(2- (2,2,2-trichloroacetamido)phenyl)acetamide molecule were calculated by using the CrystalExplorer 17 [40]. The Hirshfeld surfaces are mapped with different properties dnorm, shape index and curvedness. The dnorm is normalized contact distance, defined in terms of de, di and the vdW radii of the atoms. The combination of de and di in the form of a 2D fingerprint plot displays the summary of intermolecular contacts in the crystal. 3. Results and discussion 3.1. Molecular geometry The title compound was prepared according to the previously published method (Scheme 1) [21]. It was characterized by Nuclear Magnetic Resonance spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR) techniques. All the obtained characterization data agree with both the literature data [21] and the structure proposed for the title compound. The molecular structure of the 2,2,2- trichloro-N, N-bis(2-(2, 2, 2-trichloroacetamido)phenyl)acet- amide obtained by the single crystal X-ray diffraction method has been previously reported [21,22]. The compound crystal- lizes monoclinic, space group P21/n, a = 12.3377(6) Å, b = 12.3897(5) Å, c = 15.4444(7) Å, β = 93.849(2)°, V = 2355.51(18) Å3, Z = 4 and Dcalc = 1.792 g/cm3. The molecular structure of H2LNNN compound belongs to C1 point group symmetry. Figure 2 demonstrates the single crystal structure and the optimized molecular structure of H2LNNN molecule which was obtained from the GaussView 6.0 program [34]. Table 1 lists the optimized structure parameters of H2LNNN compound calculated by B3LYP, BLYP, B3PW91, mPW1PW91 and HF methods with the standard 6-31G(d,p) and 6-311G(d,p) basis sets. At the optimized geometry for H2LNNN molecule, no imaginary frequency modes were obtained, therefore a true minimum on the potential energy surface was found. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 326 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 Table 1. Optimized and experimental geometries of H2LNNN molecule in the ground state *. Parameter Experimental, Å Calculated, Å B3LYP B3PW91 BLYP HF mPW1PW 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 Bond lengths C1-C2 1.569(2) 1.580 1.580 1.575 1.573 1.595 1.597 1.564 1.563 1.571 1.569 C1-Cl25 1.761(2) 1.781 1.780 1.769 1.766 1.803 1.802 1.762 1.762 1.764 1.761 C1-Cl26 1.774(2) 1.810 1.809 1.795 1.794 1.841 1.838 1.776 1.777 1.789 1.788 C1-Cl27 1.774(2) 1.800 1.798 1.786 1.784 1.827 1.825 1.771 1.772 1.781 1.779 C2-O3 1.206(2) 1.214 1.206 1.212 1.205 1.227 1.219 1.188 1.181 1.209 1.202 C2-N4 1.356(2) 1.367 1.367 1.363 1.363 1.380 1.380 1.355 1.356 1.360 1.360 N4-C5 1.414(2) 1.412 1.412 1.406 1.405 1.423 1.423 1.412 1.412 1.403 1.402 C5-C6 1.396(2) 1.403 1.401 1.401 1.398 1.415 1.412 1.389 1.388 1.399 1.396 C5-C10 1.403(2) 1.414 1.411 1.411 1.409 1.427 1.424 1.398 1.397 1.409 1.406 C6-C7 1.392(3) 1.393 1.391 1.391 1.389 1.402 1.399 1.383 1.383 1.389 1.387 C7-C8 1.383(3) 1.393 1.390 1.391 1.388 1.403 1.400 1.381 1.380 1.389 1.386 C8-C9 1.388(2) 1.392 1.389 1.390 1.387 1.402 1.399 1.382 1.381 1.388 1.386 C9-C10 1.389(2) 1.397 1.394 1.395 1.392 1.408 1.405 1.387 1.385 1.392 1.389 C10-N11 1.442(2) 1.445 1.444 1.438 1.436 1.457 1.456 1.439 1.439 1.435 1.433 N11-C12 1.443(2) 1.445 1.444 1.438 1.435 1.458 1.457 1.437 1.437 1.435 1.433 N11-C22 1.376(2) 1.390 1.391 1.386 1.386 1.406 1.407 1.384 1.385 1.382 1.382 C12-C13 1.398(2) 1.402 1.399 1.400 1.397 1.413 1.409 1.387 1.386 1.399 1.395 C12-C17 1.403(2) 1.413 1.408 1.410 1.406 1.425 1.420 1.395 1.394 1.408 1.404 C13-C14 1.380(2) 1.390 1.388 1.388 1.386 1.400 1.398 1.383 1.383 1.386 1.384 C14-C15 1.389(2) 1.393 1.391 1.392 1.389 1.404 1.401 1.381 1.380 1.390 1.387 C15-C16 1.385(2) 1.389 1.387 1.387 1.385 1.399 1.397 1.382 1.382 1.385 1.383 C16-C17 1.395(2) 1.401 1.397 1.400 1.395 1.413 1.408 1.385 1.384 1.398 1.394 C17-N18 1.432(2) 1.425 1.427 1.418 1.419 1.434 1.436 1.428 1.428 1.415 1.416 N18-C19 1.341(2) 1.349 1.349 1.346 1.345 1.363 1.362 1.339 1.340 1.343 1.343 C19-O20 1.219(2) 1.219 1.211 1.217 1.210 1.232 1.224 1.191 1.185 1.214 1.208 C19-C21 1.561(2) 1.575 1.574 1.571 1.568 1.590 1.591 1.563 1.561 1.567 1.564 C21-Cl28 1.780(2) 1.811 1.808 1.797 1.794 1.838 1.836 1.778 1.780 1.791 1.789 C21-Cl29 1.766(2) 1.772 1.771 1.760 1.758 1.791 1.790 1.756 1.756 1.755 1.754 C21-Cl30 1.766(2) 1.808 1.807 1.794 1.792 1.841 1.839 1.777 1.777 1.788 1.786 C22-O23 1.207(2) 1.212 1.205 1.211 1.204 1.225 1.218 1.184 1.177 1.208 1.201 C22-C24 1.574(2) 1.585 1.586 1.580 1.579 1.599 1.601 1.575 1.575 1.576 1.575 C24-Cl31 1.766(2) 1.790 1.788 1.776 1.774 1.816 1.814 1.765 1.765 1.771 1.769 C24-Cl32 1.777(2) 1.812 1.808 1.798 1.794 1.842 1.838 1.776 1.776 1.792 1.788 C24-Cl33 1.779(2) 1.797 1.798 1.784 1.784 1.821 1.822 1.775 1.776 1.778 1.778 r 0.9993 0.9994 0.9993 0.9993 0.9986 0.9989 0.9994 0.9992 0.9993 0.9994 Bond angles C2-C1-Cl25 109.98(12) 109.56 109.50 109.35 109.37 109.61 109.51 109.70 109.77 109.33 109.37 C2-C1-Cl26 109.89(12) 109.46 109.48 109.47 109.41 109.71 109.75 108.41 108.43 109.42 109.32 C2-C1-Cl27 109.34(12) 109.68 109.81 109.43 109.51 109.81 110.02 110.72 110.59 109.35 109.44 Cl25-C1-Cl26 108.50(9) 108.74 108.72 108.92 108.93 108.53 108.50 108.82 108.81 108.99 109.00 Cl25-C1-Cl27 109.29(9) 109.29 109.27 109.45 109.49 109.19 109.14 108.76 108.88 109.52 109.56 Cl26-C1-Cl27 109.82(9) 110.09 110.04 110.21 110.13 109.97 109.89 110.42 110.34 110.20 110.13 C1-C2-O3 120.24(15) 119.23 119.30 119.27 119.47 119.16 119.18 118.99 119.18 119.34 119.55 C1-C2-N4 113.42(14) 114.64 114.54 114.56 114.33 114.65 114.61 115.55 115.22 114.43 114.20 O3-C2-N4 126.34(16) 126.13 126.16 126.18 126.20 126.20 126.21 125.45 125.60 126.23 126.25 C2-N4-C5 123.21(14) 124.39 124.19 124.28 124.14 124.59 124.33 122.50 122.78 124.35 124.20 N4-C5-C6 120.99(16) 122.21 122.03 122.40 122.27 122.09 121.86 120.86 121.02 122.59 122.47 N4-C5-C10 120.16(15) 119.52 119.81 119.39 119.58 119.72 120.09 120.77 120.63 119.12 119.32 C6-C5-C10 118.84(16) 118.26 118.15 118.20 118.14 118.17 118.04 118.36 118.34 118.27 118.21 C5-C6-C7 120.39(15) 120.78 120.91 120.78 120.85 120.87 121.01 121.08 121.08 120.65 120.74 C6-C7-C8 120.42(16) 120.80 120.74 120.86 120.80 120.79 120.72 120.45 120.46 120.92 120.86 C7-C8-C9 119.63(17) 118.97 118.94 118.92 118.92 119.01 118.96 118.92 118.87 118.94 118.93 C8-C9-C10 120.54(17) 120.98 121.06 120.95 120.98 121.04 121.14 121.21 121.25 120.85 120.88 C5-C10-C9 120.07(16) 120.15 120.15 120.25 120.26 120.08 120.06 119.88 119.92 120.33 120.33 C5-C10-N11 120.39(15) 121.02 121.28 120.87 121.04 121.23 121.54 121.57 121.54 120.61 120.80 C9-C10-N11 119.46(16) 118.71 118.45 118.74 118.57 118.56 118.27 118.52 118.51 118.91 118.73 C10-N11-C12 117.13(13) 116.40 116.61 116.30 116.53 116.35 116.56 117.05 117.11 116.27 116.49 C10-N11-C22 123.75(14) 123.28 122.39 123.12 122.42 123.27 122.44 119.91 119.51 123.34 122.65 C12-N11-C22 115.88(14) 116.61 116.55 116.73 116.77 116.39 116.33 115.73 115.75 116.96 116.98 N11-C12-C13 118.00(16) 118.18 118.73 118.14 118.59 118.19 118.67 119.95 120.06 117.99 118.43 N11-C12-C17 123.01(15) 123.71 122.96 123.72 123.08 123.71 123.08 121.41 121.33 123.90 123.28 C13-C12-C17 118.99(16) 118.11 118.30 118.13 118.33 118.09 118.25 118.61 118.59 118.09 118.29 C12-C13-C14 121.22(16) 121.91 121.64 121.92 121.66 121.91 121.68 121.17 121.21 121.96 121.71 C13-C14-C15 119.79(16) 119.82 119.90 119.80 119.86 119.83 119.90 120.13 120.09 119.79 119.85 C14-C15-C16 119.71(16) 119.10 119.16 119.09 119.16 119.15 119.21 119.10 119.09 119.06 119.13 C15-C16-C17 121.11(16) 121.73 121.50 121.75 121.55 121.70 121.51 121.20 121.22 121.80 121.60 C12-C17-C16 119.14(15) 119.30 119.46 119.28 119.39 119.27 119.41 119.78 119.80 119.26 119.36 C12-C17-N18 125.11(15) 125.76 124.82 125.67 124.85 125.80 124.99 123.67 123.54 125.83 125.03 C16-C17-N18 115.72(16) 114.86 115.66 115.00 115.72 114.87 115.56 116.46 116.60 114.86 115.57 C17-N18-C19 125.61(14) 127.95 126.83 127.71 126.80 128.24 127.27 124.79 124.60 127.75 126.86 N18-C19-O20 126.42(16) 126.33 126.25 126.39 126.34 126.49 126.48 125.62 125.58 126.36 126.30 N18-C19-C21 116.26(14) 114.17 114.35 113.97 114.12 114.02 114.09 115.80 115.63 113.95 114.09 O20-C19-C21 117.24(15) 119.41 119.29 119.53 119.42 119.40 119.33 118.44 118.67 119.60 119.49 C19-C21-Cl28 105.86(11) 106.40 106.09 106.34 105.92 106.43 106.26 105.40 105.34 106.40 105.96 C19-C21-Cl29 109.60(12) 110.26 110.17 110.09 110.05 110.42 110.34 110.14 110.11 110.05 110.02 C19-C21-Cl30 113.19(12) 111.82 112.24 111.71 112.05 112.10 112.46 113.34 113.32 111.49 111.84 Cl28-C21-Cl29 108.61(9) 109.90 109.85 109.99 109.94 109.91 109.81 109.99 109.95 109.98 109.94 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 327 Table 1. Continued. Parameter Experimental, Å Calculated, Å B3LYP B3PW91 BLYP HF mPW1PW 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 Cl28-C21-Cl30 110.44(9) 108.86 108.91 108.93 109.07 108.54 108.58 108.81 108.86 109.04 109.17 Cl29-C21-Cl30 109.01(9) 109.54 109.50 109.72 109.74 109.38 109.31 109.09 109.17 109.81 109.83 N11-C22-O23 122.91(16) 122.50 122.88 122.56 122.88 122.50 122.88 123.28 123.43 122.54 122.84 N11-C22-C24 119.77(14) 120.83 120.25 120.61 120.04 120.74 120.27 120.37 119.91 120.56 120.02 O23-C22-C24 117.14(15) 116.61 116.77 116.78 117.00 116.69 116.75 116.24 116.54 116.86 117.06 C22-C24-Cl31 115.16(12) 116.31 116.46 116.10 116.28 116.76 117.04 115.77 115.85 115.93 116.12 C22-C24-Cl32 109.41(12) 107.62 107.81 107.60 107.69 107.55 107.68 108.47 108.46 107.57 107.66 C22-C24-Cl33 106.30(12) 107.19 106.80 107.01 106.65 107.28 106.88 106.74 106.62 107.04 106.71 Cl31-C24-Cl32 110.36(10) 109.85 109.82 109.99 109.98 109.66 109.57 109.87 109.86 110.04 110.04 Cl31-C24-Cl33 107.66(9) 107.56 107.59 107.78 107.83 107.43 107.43 107.45 107.54 107.85 107.89 Cl32-C24-Cl33 107.59(9) 108.02 108.05 108.08 108.10 107.83 107.89 108.27 108.24 108.13 108.13 r 0.9886 0.9908 0.9885 0.9906 0.9877 0.9891 0.9851 0.9846 0.9880 0.9904 * 6-31: 6-31G(d,p); 6-311: 6-311G(d,p); The atom numbering scheme given in Figure 2(a). As a result, the unscaled calculated frequencies, reduced masses, force constants and infrared intensities are obtained. It can be said that X-ray single crystal geometrical parameters fairly well reproduced the optimized geometry when the theoretical and experimental geometry of H2LNNN compound was compared to each other. Based on this comparison, the bond lengths and angles calculated for H2LNNN compound show good agreement with experiment one. According to our calculations, the optimized bond lengths and bond angles obtained by mPW1PW91/6-311G(d,p) and B3LYP/6-311G (d,p) methods, respectively, show the best agreement with the experimental values. The largest difference between experi- mental and calculated bond lengths and bond angles are 0.020 Å and 2.05 °, respectively [21]. 3.2. Vibrational assignments The vibrational frequencies obtained by HF and DFT calculation methods are summarized in Table 2 along with the approximate description of each of the normal modes and experimental frequencies (Figure 1). Usually, anharmonicity of the incomplete incorporation of electron correlation and of the use of finite one-particle basis set causes the calculated harmonic vibrational wavenumbers to be higher than the experimental values [27]. For this reason, the scaling factors of 0.9614, 0.9679, 0.9573, 0.9631, 0.9945, 0.9934, 0.8992, 0.9051, 0.9500 and 0.9567 were used for B3LYP/6-31G(d,p), B3LYP/6-311G(d,p), B3PW91/6-31G(d,p), B3PW91/6-311G (d,p), BLYP/6-31G(d,p), BLYP/6-311G(d,p), HF/6-31G(d,p), HF/6-311G(d,p), mPW1PW91/6-31G(d,p) and mPW1PW91/ 6-311G(d,p) levels, respectively [27-33]. The vibrational bands’ assignments have been made by using both the animation option of the GaussView 6.0 graphical interface for the Gaussian programs [34] and SQM 2.0 program [36]. All the calculated spectra were found to be in good accordance with the experimental ones. Considering Table 2, it can be concluded that experimental bases better aligned with the scaled fundamentals and have a better correlation with B3LYP/6-31G(d,p) than the other calculations methods. A general and better performance of the used calculation methods can be quantitatively characterized by using the mean absolute percentage error, mean absolute error, root mean square values (RMS) and coefficients of correlation (r) between the theoretically calculated and experimentally observed vibration frequencies (Table 3). All these values were calculated in this study by the PAVF 1.0 program [37] according to Scott and Radom [27]. The RMS values were obtained in this study using Equation (1) [27,41]. The r values for all DFT methods were greater than 0.9987. These values are very close to those reported in literature [28,42,43]. The RMS error of the observed and calculated IR bands is given in Table 3. These results indicate that the fundamental frequencies calculated by the selected methods (except HF) and basis sets for H2LNNN compound show good agreement with experimental values. Especially, the B3LYP method with 6-31G(d,p) basis set has the best agreement. We observed a small difference between experimental and theoretical vibrational modes. This discrepancy is due to the formation of the intermolecular and intramolecular hydrogen bonding. Also, we note that the experimental results belong to the solid phase and the theoretical results belong to the gaseous phase. Finally, we calculated the optimal scaling factors, which are crucial for IR spectral predictions, using the PAVF 1.0 program [37]. Without accounting for different vibrations, only single- uniform scaling factors were calculated. The values obtained are 0.9588, 0.9639, 0.9545, 0.9594, 0.9924, 0.9973, 0.8928, 0.8981, 0.9473 and 0.9522 for the B3LYP/6-31G(d,p), B3LYP/ 6-311G(d,p), B3PW91/6-31G(d,p), B3PW91/6-311G(d,p), B- LYP/6-31G(d,p), B-LYP/6-311G(d,p), HF/6-31G(d,p), HF/6- 311G(d,p), mPW1PW91/6-31G(d,p) and mPW1PW91/ 6-311G (d,p) methods, respectively. They are very close to those recommended by Scott and Radom [27] for the same level of theory. ( )2exp1RMS 1 n calc i i i v v n = M M ∑ (1) The νNH stretching vibration bands are generally observed in the 3500-3000 cm-1 region of the FT-IR spectrum for heterocyclic compounds [23,44,45]. In this study, the stretching vibration mode of νNH groups of H2LNNN molecule in FT-IR spectrum were observed at 3335 and 3291 cm-1. νNH stretching vibration modes were calculated by B3LYP/6- 31G(d,p) method as 3469 and 3296 cm-1 (Table 2). The differences between the experimentally observed and theoretically calculated νNH stretching vibration bands were found to be 134 and 5 cm-1, respectively, and these differences were related to the hydrogen bond N-H⋯O=C occurring between the molecules [23,44,45]. The hydrogen bond (N- H⋯O=C) between the molecules of H2LNNN was also confirmed by the deviation in the νC=O stretching vibration mode. The νC=O stretching vibration modes were observed at 1728, 1725 and 1706 cm-1, whereas theoretically related νC=O stretching vibration modes were calculated at 1737, 1727 and 1710 cm-1, respectively. The differences between the calculated and observed stretching modes are 9, 2 and 4 cm-1, respectively (Table 2). These results are confirmed by the presence of intermolecular hydrogen bonds in the single crystal structure of the compound [21]. The characteristic νCH stretching vibrations of aromatic structure are expected to appear in 3000-3100 cm-1 frequency ranges. The νCH stretching vibrations of the title compound were assigned to seven bands observed at 3155, 3112, 3101, 3095, 3082, 3078, and 3064 cm-1 in the infrared spectrum. The B3LYP/6-31G(d,p) calculated theoretical wave-numbers of these bands reproduced the experimental ones very well. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 328 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 Table 2. Vibrational wavenumbers obtained for H2LNNN at 6-31G(d,p) level. No Exp. IR (cm-1) B3LYP Assignments, PED (%) Unscaled (cm-1) Scaled (cm-1) Scaled (cm-1) IR Int. (km/mol) 1 3335 3608 3469 3460 70.00 νNH18, 100 2 3291 3428 3296 3287 424.28 νNH4, 99 3 3155 3275 3149 3140 2.26 νCHarom, 99, sym 4 3112 3233 3108 3100 2.46 νCHarom, 90, sym 5 3101 3224 3099 3091 3.30 νCHarom, 96, sym 6 3095 3217 3093 3084 11.33 νCHarom, 86, asym 7 3082 3210 3086 3078 16.69 νCHarom, 99, asym 8 3078 3202 3078 3070 4.54 νCHarom, 96, asym 9 3078 3195 3072 3064 2.72 νCHarom, 96, asym 10 3064 3189 3066 3057 2.83 νCHarom, 95, asym 11 1728 1806 1737 1732 109.6 νCO3, 76 12 1725 1796 1727 1722 418.59 νCO19, 65 13 1706 1778 1710 1705 109.42 νCO22, 81 14 1596 1657 1593 1589 7.90 νCCarom, 58 15 1589 1654 1590 1586 1.69 νCCarom, 53 16 1586 1646 1583 1579 85.73 νCCarom, 38 + δCNH, 12 + δCCC, 11 17 1582 1638 1574 1570 4.65 νCCarom, 41 + δCNH, 12 18 1524 1586 1525 1521 278.07 νCCarom, 12 + δCNH, 44 19 1498 1568 1507 1503 173.34 νNCarom, 16 + δCNH, 54 20 1487 1537 1477 1473 154.21 νNCarom, 21 + δCHarom, ipb, 52 + δCCC, 21 21 1452 1524 1465 1462 47.67 δCNH, 22 + δCCH, 45 22 1440 1490 1432 1428 66.52 δCHarom, ipb, 43 + νCCarom, 24 23 1428 1480 1423 1419 27.35 δCHarom, ipb, 48 + νCCarom, 22 24 1313 1363 1310 1307 23.77 νCCarom, 63 25 1293 1342 1290 1286 93.02 νCCarom, 69 26 1278 1330 1278 1275 79.08 νCCarom, 21 + νCN, 14 + δCHarom, ipb, 41 27 1268 1323 1272 1268 37.52 νCCarom, 20 + νCN, 10 + δCHarom, ipb, 45 28 1253 1297 1247 1243 55.48 νCN, 38 + δCHarom, ipb, 21 29 1231 1283 1233 1230 183.56 νCCarom, 19 + νCN, 24 + δCNH, 20 30 1224 1275 1226 1222 92.55 νCN, 35 + δCNH, 11 + δCHarom, ipb, 28 31 1200 1254 1206 1203 20.01 νCN, 27 + δCHarom, ipb, 33 32 1176 1220 1173 1169 57.81 νCN, 35 + δCHarom, ipb, 42 33 1169 1218 1171 1168 19.64 νCN, 28 + δCHarom, ipb, 45 + νCCCl, 11 34 1156 1199 1153 1150 11.33 νCCarom, 24 + δCHarom, ipb, 45 + νCCCl, 14 35 1145 1196 1150 1146 0.79 νCCarom, 14 + δCHarom, ipb, 46 36 1145 1192 1146 1143 5.41 νCCarom, 10 + δCHarom, ipb, 48 + νCCCl, 13 37 1103 1147 1103 1100 12.18 νCCarom, 11 + δCHarom, ipb, 42 38 1087 1125 1081 1078 11.24 νCCarom, 11 + δCHarom, ipb, 42 39 1049 1087 1045 1042 4.15 νCCarom, 45 + νCCCl, 10 40 1038 1084 1042 1039 3.98 νCCarom, 42 41 952 997 958 956 0.27 δCHarom, opb, 75 42 952 993 954 952 0.20 δCHarom, opb, 79 43 945 986 948 945 3.82 δCHarom, opb, 35 + δCCC, 21 + νCC, 20 + νCCCl, 12 44 942 977 939 936 0.50 νCCCl, 32 + δOCN, 23 + νCC, 35 45 921 963 926 923 2.13 δCHarom, opb, 24 + νCCCl, 19 46 918 958 921 918 0.84 δCHarom, opb, 35 + νCCCl, 12 + δCNH, 28 47 918 956 919 916 2.05 δCHarom, opb, 46 + νCCCl, 13 48 882 921 885 883 11.51 δCCCring, 65 + νCN, 21 + δCHarom, opb, 12 49 860 897 862 860 22.27 δCHarom, opb, 46 + νCC, 11 + δCCN, 20 50 856 887 852 850 67.09 δCHarom, opb, 22 + δCCCring, 35 + νCCCl, 11 51 842 881 847 844 34.39 δCHarom, opb, 51 + δCCN, 22 52 840 873 839 837 31.59 δCHarom, opb, 58 + δCCN, 24 53 808 834 802 800 90.63 νCCl, 61 + δCCN, 17 + δNH, opb, 16 54 798 823 791 789 76.55 νCCl, 52 + δNH, opb, 40 55 786 814 782 780 67.37 νCCl, 50 + δCHarom, opb, 22 + δCCCring, 12 56 773 807 776 773 63.70 νCCl, 44 + δCHarom, opb, 20 + δCCCring, 15 57 770 805 773 771 52.04 γC-CCarb, 39 + νCCl, 16 58 759 796 766 764 127.74 γC-CCarb, 38 + νCCl, 17 59 752 783 753 751 27.65 δCHarom, opb, 71 60 749 780 750 748 63.3 δCHarom, opb, 64 61 740 774 744 742 41.66 δCHarom, opb, 62 + γC-CCarb, 12 62 735 761 732 730 42.12 δCHarom, opb, 60 + γNH, 17 + δCCCring, 10 63 723 752 723 721 52.11 δCHarom, opb, 44 + γC-CCarb, 42 64 716 742 713 711 4.30 γNH, 58 + δCHarom, opb, 13 65 702 735 706 705 18.97 γNH, 69 + δCHarom, opb, 23 66 679 712 684 682 25.34 γNH, 47 + δCHarom, opb, 21 + νCCl, 15 67 660 675 649 647 39.47 δCCCring, 38 + δCHarom, opb, 21 + δNCO, 11 68 636 659 634 632 65.29 δCCCring, 20 + γC, 45 + νCCl, 19 69 621 651 626 624 62.23 δCCCring, 10 + γC, 25 + νCCl, 46 70 612 646 621 620 119.36 δCCCring, 11 + γC, 27 + νCCl, 40 71 591 622 598 596 26.63 δCCCring, 39 + γC, 21 72 571 599 576 574 41.29 δCCCring, 44 + γC, 22 73 559 583 560 559 9.81 δCCCring, 47 + γC, 26 74 - 559 538 536 6.49 γC, 26 + γNH, 37 + δCCCring, 22 75 - 556 535 533 3.04 γC, 33 + γNH, 31 + δCCCring, 20 76 - 535 515 513 25.16 γC, 30 + γNH, 19 77 - 521 501 499 13.95 γC, 21 + γNH, 27 78 - 501 481 480 3.35 γC, 29 + τCCring, 43 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 329 Table 2. Continued. No Exp. IR (cm-1) B3LYP Assignments, PED (%) Unscaled (cm-1) Scaled (cm-1) Scaled (cm-1) IR Int. (km/mol) 79 - 484 465 464 7.61 τCCring, 48 + γNH, 12 80 - 470 452 450 6.14 δCCN, 40 + γC, 36 81 - 444 427 426 5.72 γNH, 25 + δCCN, 30 82 - 429 412 411 0.85 νCClsym, 54 + δCNC, 32 83 - 422 406 405 6.22 δCCO, 28 + νCClsym, 21 + δCCN, 12 84 - 416 400 399 3.59 δNCO, 23 + νCClsym, 27 + δCCN, 20 85 - 377 362 361 0.95 δClCCl, 35 + δCCCring, 20 + νCCl, 17 86 - 369 355 354 2.15 δClCCl, 40 + δCCCring, 22 + νCCl, 26 87 - 359 345 344 1.01 δClCCl, 40 + δCCCring, 22 88 - 345 331 331 0.25 γCring, 41 + τCC, 40 89 - 336 323 322 3.45 δCCCring, 14 + τCC, 12 + δOCC, 21 90 - 315 302 302 3.46 γCring, 26 + γCN, 25 + τCC, 20 91 - 304 293 292 2.18 τCC, 22 + γCN, 20 + γC, 15 + δClCClscis, 32 92 - 295 284 283 1.73 δCCClscis, 36 + δNCO, 19 93 - 288 277 276 0.79 δClCClscis, 31 + τCC, 29 94 - 283 272 272 0.99 τCC, 22 + δClCCl, 38 95 - 280 269 269 0.58 γC, 26 + δClCClscis, 39 96 - 267 256 256 0.57 γNH, 31 + δCCClscis, 40 τCC, 18 97 - 259 249 248 3.13 γNH, 27 + δCCClscis, 42 98 - 239 230 229 1.18 δCCClscis, 44 + τNC, 22 + γC, 28 99 - 230 221 220 0.35 δCCCl, 33 + τNC, 16 + γC, 22 100 - 221 213 212 0.23 δCCCl, 40 + τNC, 16 101 - 203 195 194 0.20 δCCCltwist, 29 + τNC, 18 102 - 197 190 189 2.35 τCC, 32 103 - 187 180 180 7.45 τCCCl, 32 104 - 167 161 160 1.52 δNCCring, 41 + τNC, 19 + δCCCltwist, 20 105 - 166 159 159 0.47 τNC, 18 + τCCCl, 10 + δCNC, 12 + δCCCltwist, 12 106 - 157 151 150 2.73 τNCring, 15 + τCCCl, 15 + δCNC, 14 107 - 142 137 136 1.34 τNCring, 26 + τCCCl, 11 + δCNC, 10 108 - 141 136 136 2.38 τNCring, 26 + τCN, 15 + δCNC, 13 109 - 130 125 125 4.47 τNCring, 47 + τCN, 13 + δCCClwagg, 12 110 - 100 96 96 0.92 τNCring, 24 + τCN, 32 111 - 96 92 92 1.36 τCN, 30 + δCNC, 15 + δCCClwagg, 12 112 - 91 88 88 0.81 τCN, 28 + δCNC, 12 113 - 80 77 77 1.23 τCN, 44 + τCC, 10 + τCCCl, 11 + δCNC, 15 114 - 69 67 66 0.23 τCC, 35 + δCNC, 15 115 - 47 46 45 0.28 τCN, 44 + τCC, 10 + τCCCl, 11 116 - 47 45 45 0.43 τCN, 11 + τCC, 40 117 - 45 43 43 0.45 τCN, 51 118 - 42 40 40 0.27 τNCring, 56 + δCCClrock, 12 119 - 35 33 33 0.49 τCN, 28 + τCC, 38 120 - 31 30 30 0.35 τCC, 39 + τNCring, 37 + δCCClrock, 13 121 - 28 27 27 0.45 τCN, 40 + τCC, 25 + δCCClrock, 15 122 - 19 18 18 0.03 τCN, 41 + τCC, 37 + δCCClrock, 16 123 - 15 14 14 0.38 τCN, 43 r 0.9998 0.9998 0.9998 Mean absolute percentage error 4.1492 0.4407 0.4648 Mean absolute error 55.9474 5.8136 6.6174 RMS 52.4182 12.5792 12.1672 Scaling factor 1.000 0.9614 0.9588 * ν, stretching; δ, in-plane bending; γ, out-of-plane bending; τ, torsion; ipb: in-plane bending; opb: out-of-plane bending; scis: scissoring; wagg: wagging; twist: twisting; rock: rocking; sym, symmetric; asym, asymmetric; arom: aromatic; carb: carbonyl group; PED less than 10% are not shown. The differences between experimentally observed and theoretically calculated νCH are about 6, 4, 2, 2, 4, 6 and 2 cm-1. 3.3. Thermodynamic parameters and molecular properties Table 4 lists the calculated values of some thermodynamic parameters (such as zero-point vibrational energy, thermal corrections to energy, enthalpy and entropy) of the title compound. The minimum and maximum energy obtained from the geometric optimization of the title compound were calculated as -5224.102 a.u. for the B3LYP/6-311G(d,p) and - 5210.664 a.u. for HF/6-31G(d,p) method. The calculated energy difference for these two extreme values is only -13.438 a.u. The biggest value of zero-point vibrational energy is 176.359 kcal/mol obtained at HF/6-31G(d,p) whereas the smallest one is 155.648 kcal/mol obtained at BLYP/6- 311G(d,p). The total energies are found to decrease with the increase of basis set dimension [21]. The natural population analysis (NPA) and Mulliken charge values calculated for H2LNNN molecule are given in Tables 5 and 6, respectively. NPA and Mulliken atomic charge calculation results showed that the carbon atom in the carbonyl group (C19, 0.8379 (HF/6-31G(d, p)) have the highest positive charge. In addition, it was also found that the oxygen atom in the molecule (O2O, -0.7061 (HF/6-31G(d,p)) was charged with negative charge as expected and the C19- O20 carbonyl group shared the highest negative and positive charges of the molecule [21]. 3.4. Hirshfeld surfaces analysis The supramolecular architecture in the H2LNNN has been stabilized by hydrogen bonding, halogen···halogen and C- halogen···π (Cl···Cl and C-Cl···π) interactions. These interactions have further been investigated with the help of Hirshfeld surface analyses. Molecular Hirshfeld surface calculations were performed using the Crystal Explorer 17 program [40]. All Hirshfeld surfaces were created using crystallographically determined coordinates of the atoms in the compound and a standard (high) surface resolution [21,40]. The dnorm, de, di, curvedness and shape index surfaces of the H2LNNN are shown in Figure 3. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 330 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 Table 3. Statistical comparison of theoretical and experimental vibrational wavenumbers of H2LNNN molecule on the used method and basis set *. Method B3LYP B3LYP×SF B3LYP×CSF B3LYP B3LYP×SF B3LYP×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9998 0.9998 0.9998 0.9998 0.9998 0.9998 Mean absolute percentage error 4.1492 0.4407 0.4648 3.7561 0.6706 0.6432 Mean absolute error 55.9474 5.8136 6.6174 49.3742 8.068 8.583 RMS 52.4182 12.5792 12.1672 46.3699 14.1371 13.2612 Scaling factor 1.000 0.9614 0.9588 1.000 0.9679 0.9639 Method B3PW91 B3PW91×SF B3PW91×CSF B3PW91 B3PW91×SF B3PW91×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9998 0.9998 0.9998 0.9997 0.9997 0.9997 Mean absolute percentage error 4.8639 0.6422 0.6198 4.5332 0.8356 0.7321 Mean absolute error 63.8512 8.1063 8.5868 57.8698 9.4337 9.5315 RMS 58.0298 13.5511 13.1117 52.0289 14.3824 13.6441 Scaling factor 1.000 0.9573 0.9545 1.000 0.9631 0.9594 Method BLYP BLYP×SF BLYP×CSF BLYP BLYP×SF BLYP×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9998 0.9998 0.9998 0.9998 0.9998 0.9998 Mean absolute percentage error 1.0796 1.2914 1.4114 1.1965 1.5784 1.3314 Mean absolute error 14.5717 14.9083 15.6016 14.694 17.0247 15.3341 RMS 19.0646 16.9564 16.7738 17.6689 17.9821 17.3735 Scaling factor 1.000 0.9945 0.9924 1.000 0.9934 0.9973 Method HF HF×SF HF×CSF HF HF×SF HF×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9988 0.9988 0.9988 0.9987 0.9987 0.9987 Mean absolute percentage error 13.8217 3.1296 2.842 13.1963 3.2733 2.9543 Mean absolute error 171.1416 36.0217 34.4972 162.4022 37.3614 35.673 RMS 146.3035 34.4368 33.3818 138.9225 35.5478 34.3323 Scaling factor 1.000 0.8992 0.8928 1.000 0.9051 0.8981 Method mPW1PW mPW1PW×SF mPW1PW×CSF mPW1PW mPW1PW×SF mPW1PW×CSF Basis set 6-31G(d,p) 6-311G(d,p) r 0.9997 0.9997 0.9997 0.9997 0.9997 0.9997 Mean absolute percentage error 5.8816 0.8467 0.7881 5.5286 1.1156 0.9195 Mean absolute error 75.9789 10.3949 10.5058 69.7615 12.1907 11.5181 RMS 67.5244 14.5200 14.1232 61.3765 15.8572 14.8462 Scaling factor 1.000 0.9500 0.9473 1.000 0.9567 0.9522 * SF: Scaling factor, CSF: Calculated Scaling factor in this research. Table 4. The calculated thermodynamic parameters of H2LNNN molecule. Thermodynamic parameters (298 K) B3LYP B3PW91 BLYP HF mPW1PW91 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 SCF energy (a.u.) -5223.60 -5224.10 -5222.71 -5223.19 -5223.10 -5223.64 -5210.66 -5211.10 -5223.43 -5223.90 Total energy (Thermal) Etotal (kcal/mol) 183.157 182.462 183.993 183.366 177.481 176.826 195.475 194.548 185.283 184.630 Entropy, S (cal/mol.K) 214.608 215.056 213.907 214.285 219.796 221.013 204.953 205.177 212.368 213.090 Vibrational energy, Evib (kcal/mol) 181.379 180.685 182.216 181.588 175.704 175.048 193.697 192.770 183.506 182.852 Zero-point vib. energy, Eo (kcal/mol) 162.761 162.034 163.702 163.060 156.360 155.648 176.359 175.390 165.152 164.478 Rotational constant (GHz) A 0.09533 0.09686 0.09607 0.09805 0.09284 0.09397 0.09843 0.09881 0.09669 0.09864 B 0.08906 0.08832 0.08969 0.08941 0.08699 0.08610 0.08721 0.08757 0.09082 0.09047 C 0.06626 0.06592 0.06671 0.06660 0.06474 0.06428 0.06441 0.06481 0.06754 0.06733 Dipole moment (Debye) µx -0.7187 -0.7558 -0.7122 -0.7230 -0.6796 -0.6568 -1.2741 -1.1995 -0.6052 -0.6577 µy 1.3092 1.4144 1.2573 1.2338 1.4447 1.6122 1.3005 1.3091 1.2777 1.2135 µz 4.2015 4.1790 4.2092 4.0901 4.3433 4.3486 3.2937 3.4107 4.2370 4.1058 µTotal 4.4590 4.4761 4.4503 4.3329 4.6274 4.6841 3.7634 3.8452 4.4666 4.3316 Entropy (cal/mol.K) Total 214.608 215.056 213.907 214.285 219.796 221.013 204.953 205.177 212.368 213.090 Translational 45.208 45.208 45.208 45.208 45.208 45.208 45.208 45.208 45.208 45.208 Rotational 37.589 37.586 37.567 37.552 37.661 37.667 37.606 37.592 37.536 37.523 Vibrational 131.811 132.262 131.132 131.525 136.927 138.139 122.139 122.377 129.623 130.358 * 6-31: 6-31G(d,p); 6-311: 6-311G(d,p). The 3D di surface was mapped using 0.956 (red) -2.976 (blue), de surface 0.957 (red) -2.977 (blue), and the dnorm surface -0.285 (red) -1.582 (blue) using fixed color scales (Figure 3) [21,46]. The dnorm is a ratio encompassing the distances of any surface point to the nearest interior (di) and exterior (de) atom and the van der Waals (vdW) radii of the atoms and calculated using Equation (2) [21,40,46-48]. vdWvdW e ei i norm vdW vdW i e d rd rd r r MM = + (2) where, vdW ir and vdW er are the vdW radii of the atoms. Feature dnorm is generally visualized as a color range from red (dnorm < 0), if the distance between interacting atoms is less than a sum of vdW radii, through white (dnorm = 0) to blue (dnorm > 0). 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 331 Table 5. The natural charges of the atoms of H2LNNN molecule determined by natural bond analysis (NBO) *. Atom Charge B3LYP B3PW91 BLYP HF mPW1PW91 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 C1 -0.2245 -0.1926 -0.2468 -0.2054 -0.2219 -0.2046 -0.2030 -0.1415 -0.2486 -0.2036 C2 0.6672 0.6546 0.6627 0.6480 0.6271 0.6202 0.8215 0.7960 0.6717 0.6557 O3 -0.5706 -0.5722 -0.5680 -0.5691 -0.5379 -0.5440 -0.6702 -0.6569 -0.5743 -0.5742 N4 -0.6418 -0.6342 -0.6434 -0.6354 -0.6113 -0.6070 -0.7401 -0.7185 -0.6501 -0.6418 C5 0.1720 0.1751 0.1700 0.1715 0.1627 0.1672 0.2031 0.2081 0.1725 0.1738 C6 -0.2417 -0.2047 -0.2506 -0.2104 -0.2382 -0.2033 -0.2279 -0.1872 -0.2525 -0.2122 C7 -0.2154 -0.1721 -0.2235 -0.1769 -0.2153 -0.1748 -0.2029 -0.1517 -0.2231 -0.1761 C8 -0.2396 -0.1991 -0.2482 -0.2042 -0.2349 -0.1969 -0.2341 -0.1882 -0.2499 -0.2055 C9 -0.2399 -0.2102 -0.2487 -0.2171 -0.2389 -0.2110 -0.2336 -0.1950 -0.2483 -0.2164 C10 0.0965 0.1147 0.0921 0.1115 0.0968 0.1152 0.1120 0.1266 0.0911 0.1106 N11 -0.4700 -0.5028 -0.4682 -0.4989 -0.4440 -0.4796 -0.5784 -0.6057 -0.4738 -0.5037 C12 0.1492 0.1630 0.1458 0.1587 0.1431 0.1574 0.1858 0.1965 0.1465 0.1591 C13 -0.2309 -0.1996 -0.2390 -0.2047 -0.2280 -0.1986 -0.2350 -0.1968 -0.2398 -0.2051 C14 -0.2221 -0.1775 -0.2303 -0.1828 -0.2206 -0.1791 -0.2024 -0.1525 -0.2311 -0.1833 C15 -0.2250 -0.1845 -0.2336 -0.1886 -0.2224 -0.1840 -0.2256 -0.1778 -0.2342 -0.1890 C16 -0.2349 -0.1937 -0.2430 -0.1995 -0.2323 -0.1942 -0.2150 -0.1713 -0.2443 -0.2004 C17 0.1427 0.1483 0.1395 0.1449 0.1390 0.1461 0.1500 0.1581 0.1402 0.1456 N18 -0.6204 -0.6051 -0.6228 -0.6034 -0.5931 -0.5809 -0.7326 -0.7030 -0.6270 -0.6069 C19 0.6806 0.6634 0.6745 0.6553 0.6399 0.6287 0.8379 0.8086 0.6836 0.6632 O20 -0.6094 -0.6165 -0.6050 -0.6120 -0.5745 -0.5860 -0.7061 -0.6988 -0.6127 -0.6185 C21 -0.2249 -0.1906 -0.2469 -0.2032 -0.2221 -0.2025 -0.2040 -0.1415 -0.2487 -0.2015 C22 0.6725 0.6651 0.6671 0.6580 0.6308 0.6280 0.8327 0.8144 0.6761 0.6660 O23 -0.5559 -0.5568 -0.5521 -0.5535 -0.5230 -0.5288 -0.6387 -0.6272 -0.5595 -0.5596 C24 -0.2190 -0.1901 -0.2404 -0.2023 -0.2162 -0.2011 -0.2029 -0.1474 -0.2418 -0.2005 Cl25 0.0686 0.0639 0.0754 0.0689 0.0680 0.0670 0.0561 0.0435 0.0764 0.0688 Cl26 0.0216 0.0193 0.0320 0.0255 0.0128 0.0163 0.0300 0.0153 0.0331 0.0253 Cl27 0.0475 0.0439 0.0555 0.0492 0.0433 0.0442 0.0399 0.0263 0.0570 0.0494 Cl28 0.0378 0.0369 0.0458 0.0424 0.0339 0.0365 0.0392 0.0258 0.0463 0.0418 Cl29 0.0884 0.0824 0.0953 0.0869 0.0911 0.0892 0.0704 0.0571 0.0956 0.0862 Cl30 0.0331 0.0260 0.0416 0.0324 0.0228 0.0204 0.0261 0.0116 0.0448 0.0342 Cl31 0.0581 0.0564 0.0672 0.0636 0.0532 0.0556 0.0499 0.0395 0.0686 0.0639 Cl32 0.0337 0.0330 0.0423 0.0389 0.0261 0.0299 0.0387 0.0269 0.0437 0.0390 Cl33 0.0588 0.0533 0.0664 0.0583 0.0568 0.0560 0.0475 0.0340 0.0679 0.0586 H34 0.4659 0.4476 0.4706 0.4522 0.4584 0.4423 0.4783 0.4465 0.4719 0.4535 H35 0.2772 0.2417 0.2858 0.2473 0.2742 0.2415 0.2641 0.2209 0.2868 0.2480 H36 0.2492 0.2085 0.2576 0.2131 0.2471 0.2092 0.2417 0.1935 0.2582 0.2132 H37 0.2490 0.2097 0.2574 0.2145 0.2469 0.2102 0.2418 0.1953 0.2580 0.2146 H38 0.2566 0.2203 0.2654 0.2269 0.2551 0.2215 0.2460 0.2020 0.2662 0.2271 H39 0.2607 0.2256 0.2698 0.2319 0.2583 0.2258 0.2540 0.2115 0.2705 0.2321 H40 0.2511 0.2109 0.2595 0.2157 0.2490 0.2115 0.2432 0.1952 0.2601 0.2158 H41 0.2510 0.2111 0.2592 0.2154 0.2490 0.2117 0.2427 0.1956 0.2598 0.2156 H42 0.2485 0.2121 0.2569 0.2169 0.2462 0.2125 0.2436 0.1984 0.2573 0.2167 H43 0.4480 0.4150 0.4546 0.4194 0.4425 0.4119 0.4557 0.4135 0.4555 0.4198 * 6-31: 6-31G(d,p); 6-311: 6-311G(d,p). dnorm (front) Shape index (front) di (front) de (front) Curvedness (front) dnorm (back) Shape index (back) di (back) de (back) Curvedness (back) Figure 3. Hirshfeld surfaces mapped with dnorm, shape index, di, de and curvedness for H2LNNN molecule. The fingerprint plot derived from the Hirshfeld surface is a 2D map that describes the type and quantitative amount of intermolecular interactions surrounding a molecule in a crystal lattice. The combination of the di and de functions in the form of a 2D fingerprint graph provides a summary of intermolecular contacts within the crystal. The large red regions seen in the dnorm maps in Figure 4a represent strong H⋯O/O⋯H contacts. These contacts are attributed to N-H⋅⋅⋅O and C-H⋅⋅⋅O hydrogen bonds, which can also be seen in the 2D fingerprint plots as a pair of symmetrical spikes at de + di ≈ 2.2 Å for the N-H⋅⋅⋅O interactions, and de + di ≈ 3.0 Å for the C-H⋅⋅⋅O interactions. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 332 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 Table 6. Mulliken charges of the atoms of H2LNNN molecule *. Atom Charge B3LYP B3PW91 BLYP HF mPW1PW91 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 6-31 6-311 C1 -0.3878 -0.4649 -0.4569 -0.5276 -0.3586 -0.4528 -0.4048 -0.3923 -0.4685 -0.5326 C2 0.6395 0.4897 0.6527 0.5171 0.5966 0.4449 0.8018 0.6579 0.6643 0.5276 O3 -0.4480 -0.3114 -0.4492 -0.3201 -0.4179 -0.2762 -0.5397 -0.4266 -0.4555 -0.3259 N4 -0.6368 -0.4570 -0.6594 -0.4837 -0.5809 -0.4136 -0.8184 -0.6047 -0.6727 -0.4916 C5 0.3349 0.2574 0.3430 0.2798 0.3265 0.2417 0.3310 0.2916 0.3461 0.2855 C6 -0.0958 -0.0623 -0.1247 -0.0681 -0.0797 -0.0601 -0.1208 -0.0514 -0.1269 -0.0650 C7 -0.0916 -0.0856 -0.1294 -0.0960 -0.0651 -0.0798 -0.1475 -0.0758 -0.1347 -0.0933 C8 -0.0917 -0.0803 -0.1280 -0.0867 -0.0640 -0.0736 -0.1551 -0.0818 -0.1337 -0.0846 C9 -0.0913 -0.0398 -0.1187 -0.0470 -0.0734 -0.0315 -0.1456 -0.0581 -0.1199 -0.0435 C10 0.1374 -0.0607 0.1086 -0.0980 0.1469 -0.0538 0.1656 0.0294 0.1018 -0.1065 N11 -0.6031 -0.4362 -0.6079 -0.4453 -0.5511 -0.3910 -0.8135 -0.6306 -0.6215 -0.4547 C12 0.2820 0.1549 0.2767 0.1522 0.2736 0.1389 0.3004 0.2287 0.2785 0.1559 C13 -0.1044 -0.0532 -0.1314 -0.0576 -0.0855 -0.0482 -0.1515 -0.0659 -0.1346 -0.0561 C14 -0.0894 -0.0812 -0.1267 -0.0921 -0.0629 -0.0741 -0.1407 -0.0733 -0.1321 -0.0908 C15 -0.0813 -0.0755 -0.1187 -0.0837 -0.0533 -0.0695 -0.1505 -0.0793 -0.1243 -0.0806 C16 -0.1202 -0.0721 -0.1528 -0.0834 -0.1000 -0.0674 -0.1323 -0.0532 -0.1571 -0.0840 C17 0.3058 0.1960 0.3032 0.2094 0.3016 0.1868 0.2713 0.2278 0.3056 0.2151 N18 -0.5842 -0.4239 -0.6079 -0.4457 -0.5307 -0.3809 -0.7828 -0.5914 -0.6177 -0.4515 C19 0.6528 0.5055 0.6604 0.5188 0.6082 0.4654 0.8222 0.6678 0.6726 0.5270 O20 -0.4740 -0.3510 -0.4708 -0.3534 -0.4393 -0.3129 -0.5695 -0.4648 -0.4801 -0.3608 C21 -0.3906 -0.4546 -0.4598 -0.5136 -0.3614 -0.4462 -0.3998 -0.3641 -0.4721 -0.5194 C22 0.6178 0.4376 0.6231 0.4474 0.5754 0.4029 0.7876 0.5924 0.6349 0.4553 O23 -0.4403 -0.2864 -0.4342 -0.2878 -0.4142 -0.2566 -0.5087 -0.3851 -0.4404 -0.2931 C24 -0.3670 -0.4258 -0.4326 -0.4810 -0.3401 -0.4190 -0.3827 -0.3427 -0.4441 -0.4856 Cl25 0.0836 0.0863 0.1038 0.1024 0.0738 0.0836 0.0910 0.0609 0.1080 0.1035 Cl26 0.0338 0.0418 0.0568 0.0610 0.0183 0.0323 0.0575 0.0348 0.0603 0.0629 Cl27 0.0632 0.0707 0.0839 0.0882 0.0514 0.0646 0.0711 0.0462 0.0881 0.0901 Cl28 0.0566 0.0719 0.0771 0.0896 0.0453 0.0649 0.0702 0.0526 0.0805 0.0913 Cl29 0.1078 0.1127 0.1281 0.1282 0.1008 0.1130 0.1076 0.0823 0.1318 0.1288 Cl30 0.0577 0.0573 0.0773 0.0742 0.0414 0.0472 0.0607 0.0270 0.0832 0.0787 Cl31 0.0781 0.0834 0.1016 0.1040 0.0638 0.0753 0.0914 0.0582 0.1059 0.1062 Cl32 0.0481 0.0646 0.0683 0.0829 0.0339 0.0545 0.0676 0.0522 0.0723 0.0853 Cl33 0.0732 0.0809 0.0934 0.0975 0.0630 0.0774 0.0771 0.0562 0.0979 0.0994 H34 0.3393 0.3156 0.3523 0.3194 0.3125 0.2996 0.4081 0.3440 0.3578 0.3211 H35 0.1415 0.1388 0.1785 0.1524 0.1124 0.1283 0.2021 0.1350 0.1843 0.1506 H36 0.1019 0.1061 0.1378 0.1154 0.0748 0.0978 0.1677 0.1095 0.1435 0.1138 H37 0.0995 0.1035 0.1357 0.1125 0.0724 0.0953 0.1664 0.1072 0.1413 0.1106 H38 0.1145 0.1276 0.1505 0.1436 0.0882 0.1179 0.1837 0.1284 0.1559 0.1424 H39 0.1187 0.1309 0.1563 0.1476 0.0909 0.1210 0.1904 0.1346 0.1620 0.1469 H40 0.1051 0.1076 0.1410 0.1163 0.0779 0.0994 0.1710 0.1109 0.1466 0.1144 H41 0.1042 0.1067 0.1400 0.1154 0.0771 0.0986 0.1688 0.1092 0.1456 0.1135 H42 0.1056 0.1111 0.1424 0.1217 0.0783 0.1038 0.1746 0.1098 0.1478 0.1197 H43 0.2946 0.2632 0.3164 0.2736 0.2733 0.2522 0.3565 0.2866 0.3192 0.2740 * 6-31: 6-31G(d,p); 6-311: 6-311G(d,p). (b) (a) (c) Figure 4. (a) A view of dnorm Hirshfeld surface for close N–H⋯O and C-H⋯O contacts (b) Decomposed fingerprint plot for N–H⋯O contacts. (c) Decomposed fingerprint plot for C–H⋯O contacts. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 333 (a) (b) Figure 5. (a) A view of dnorm Hirshfeld surface for close Cl⋯H contacts (b) Decomposed fingerprint plot for Cl⋯H contacts. (a) (b) Figure 6. (a) A view of dnorm Hirshfeld surface for close Cl⋯Cl contacts (b) Decomposed fingerprint plot for Cl⋯Cl contacts. (a) (b) Figure 7. (a) A view of dnorm Hirshfeld surface for close C-Cl⋯π contacts (b) Decomposed fingerprint plot for C-Cl⋯π contacts. The H⋯O/O⋯H contacts are important for a compound with 7.3% contribution to the Hirshfeld surface area (see Figure 4b and c). The largest portion of the total Hirshfeld surface belongs to Cl⋯H/H⋯Cl contacts with 43.3%. These interactions are represented as a pair of short spikes at de + di ≈ 2.8 Å in fingerprint plot and seen as slight red spots on the dnorm Hirshfeld Surface (Figure 5). Other important interactions that occur on the Hirshfeld surface mapped with the dnorm function of the compound H2LNNN are the Cl-Cl interaction, which contribute 18.8% to the Hirshfeld surface. In the decomposed 2D fingerprint plot, the shortest contact between Cl atoms is also shorter than the sum of vdW radii with de + di ≈ 3.4 Å. Therefore, these interactions are essential intermolecular contacts in the crystal self- assembly of the molecule (Figure 6). The C-Cl⋯π interactions, which happened between the Cl atom and the π-system of adjacent phenyl, contributing to the three-dimensional structure of the synthesized H2LNNN compound were visualized by means of the Hirshfeld surface 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 334 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 Figure 8. All contacts in the crystal lattice of the compound H2LNNN. Figure 9. Relative percentage contributions to the Hirshfeld surface area of various intermolecular contacts in H2LNNN. mapped by the shape index function. As can be seen from Figure 7, on the Hirshfeld surface mapped by the shape index function, the hollow orange areas correspond to the C- Clexternal⋯πinternal and the bumps blue areas correspond to the C-Clinternal⋯πexternal interactions. These interactions contribute 10.8% to total Hirshfeld surface and the separated 2D fingerprint plot of C-Cl⋯π interactions show that the shortest contact is de + di ≈ 3.4 Å (Figure 7b). On the other hand, H⋯H contacts, i.e. dispersion interactions, contribute 8.9% of the total number of contacts of the compound. However, the shortest H⋯H contact is de + di ≈ 2.4 Å, which is longer than the vdW radii totals. Therefore, the compound in the crystal package is not from the main intermolecular contacts. All contacts in the crystal lattice of the compound H2LNNN and the proportions of these contacts are shown in Figures 8 and 9, respectively. 4. Conclusion The ground state geometries for the H2LNNN were optimized using the HF, BLYP, B3LYP, B3PW91 and mPW1PW91 functionals with 6-31G(d,p) and 6-311G(d,p) basis sets. The harmonic vibrational frequencies were also calculated and scaled values have been compared with an experimental IR spectrum. The correlation between the calculated and experimental vibration frequencies is characterized by coefficients bigger than 0.9987 for all used methods. Any discrepancy noted between the observed and the calculated frequencies may be due to the fact that the calculations have been actually done on a single molecule in the gaseous state contrary to the experimental values recorded in the presence of intermolecular interactions. The computed IR spectrum of the H2LNNN molecule is in good agreement with its observed FT-IR spectrum. The IR spectrum of the H2LNNN compound was interpreted in terms of the potential energy distribution analysis. Optimal uniform scaling factors were also calculated. On the other hand, the supra- molecular architecture of H2LNNN was investigated by the X- rays single crystal analysis and Hirshfeld surface analysis. It was found that the supramolecular structure in H2LNNN was stabilized by hydrogen bonding, halogen···halogen and C- halogen···π (Cl···Cl and C-Cl···π) interactions. Acknowledgements This study was supported by Research Fund of Mersin University in Turkey with Project Number: 2018-1-TP2-2799. 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 Aydogdu et al. / European Journal of Chemistry 10 (4) (2019) 323-335 335 Supporting information CCDC-1951022 contains the supplementary crystal- lographic data for this paper. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/, or by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033. Disclosure statement Conflict of interests: The authors declare that they have no conflict of interest. Author contributions: All authors contributed equally to this work. Ethical approval: All ethical guidelines have been adhered. Sample availability: Samples of the compounds are available from the author. Funding Mersin University http://dx.doi.org/10.13039/501100004172 ORCID İmmihan Sezen Aydogdu http://orcid.org/0000-0002-7334-0562 Ilkay Gumus http://orcid.org/0000-0002-9398-0057 Hakan Arslan http://orcid.org/0000-0003-0046-9442 References [1]. Lyaskovskyy, V.; Bruin, B. ACS Catal. 2012, 2, 270-279. [2]. Meunier, B.; Visser, S. P.; Shaik, S. Chem. Rev. 2004, 104(9), 3947- 3980. [3]. Allgeier, A. M.; Mirkin, C. A. Angew. Chem. Int. Ed. 1998, 37, 894-908. [4]. Kuchynka, D. J.; Kochi, J. K. Inorg. Chem. 1988, 27, 2574-2581. [5]. Bart, S. C.; Lobkovsky, E.; Bill, E.; Chirik, P. J. J. Am. Chem. Soc. 2006, 128(16), 5302-5303. [6]. Tondreau, A. M.; Milsmann, C.; Patrick, A. D.; Hoyt, H. M.; Lobkovsky, E.; Wieghardt, K.; Chirik, P. J. J. Am. Chem. Soc. 2010, 132(42), 15046- 15059. [7]. Bowman, A. C.; Milsmann, C.; Hojilla, A. C. 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This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry). 2019 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.10.4.323-335.1920 https://www.ccdc.cam.ac.uk/structures/ mailto:data_request@ccdc.cam.ac.uk http://dx.doi.org/10.13039/501100004172 http://orcid.org/0000-0002-7334-0562 http://orcid.org/0000-0002-9398-0057 http://orcid.org/0000-0003-0046-9442 http://hirshfeldsurface.net/ http://www.eurjchem.com/index.php/eurjchem/pages/view/terms http://creativecommons.org/licenses/by-nc/4.0 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms 1. Introduction 2. Experimental 2.1. Instrumentation 2.2. Synthesis 2.3. Calculation details 2.4. Hirshfeld surfaces analysis 3. Results and discussion 3.1. Molecular geometry 3.2. Vibrational assignments 3.3. Thermodynamic parameters and molecular properties 3.4. Hirshfeld surfaces analysis 4. Conclusion Acknowledgements Supporting information Disclosure statement Funding ORCID PrintField10: PrintField11: PrintField12: PrintField13: PrintField14: PrintField15: PrintField16: PrintField17: PrintField18: PrintField19: PrintField110: PrintField111: PrintField112: PrintField20: PrintField21: PrintField22: PrintField23: PrintField24: PrintField25: PrintField26: PrintField27: PrintField28: PrintField29: PrintField210: PrintField211: PrintField212: